Treatment of tantalum- and/or niobium-containing compounds

ABSTRACT

A process for treating a feedstock comprising tantalum- and/or niobium-containing compounds is provided. The process includes contacting the feedstock with a gaseous fluorinating agent, thereby to fluorinate tantalum and/or niobium present in the feedstock compounds. The resultant fluorinated tantalum and/or niobium compounds are recovered.

THIS INVENTION relates to the treatment of tantalum- and/orniobium-containing compounds. More particularly, the invention relatesto a process for treating a feedstock comprising tantalum- and/orniobium-containing compounds.

Tantalum and niobium are important metals for several modern hightechnology industries, including industries in the electronics andnuclear fields. The extraction of these metals from their mineralspresents unique challenges, as their minerals are not amenable to easyprocessing and they are difficult to separate from each other because oftheir very similar chemical properties.

In nature, tantalum and niobium are mainly encountered together asoxides. The most important sources of these elements are the mineralscolumbite, (Fe,Mn)Nb₂O₆, and tantalite, (Fe,Mn)Ta₂O₆. Columbitecomprises 55-78% Nb₂O₅, while tantalite comprises 42-84% Ta₂O₅. Anothersource of these elements is pyrochlore, (Na,Ca)Nb₂O₆(OH,F), whichcontains mostly niobium, with small amounts of tantalum.

These minerals are conventionally processed by digestion withconcentrated (70%) aqueous hydrofluoric acid (HF), or a mixture of HFand concentrated sulphuric acid (H₂SO₄). The tantalum and niobium valuesare extracted, separated and purified by a succession of solventextraction steps, followed by conversion to oxides or metals, dependingon the final product desired. These processes are complicated andhazardous, and produce large quantities of potentially harmful liquidwastes.

Compounding to this is the fact that tantalum minerals, in particular,contain small amounts of radioactive uranium, thorium and theirassociated daughter products, so that this complicates thetransportation of the ore as well as the handling of the waste streamsfrom the extraction process. These radioactive elements are present inthe crystal lattice, and are not removed by typical pre-treatment at themining site. The International Atomic Energy Agency (IAEA) regulationswith regard to the levels of radioactivity in materials that can betransported as normal goods limits these levels to a maximum of 10 Bq/g.Tantalum minerals more often have a radioactivity level of 40 Bq/g orhigher, and are hence classified as dangerous goods.

In terms of processing, in a raw material dissolution stage, the niobiumand tantalum are normally dissolved in a hydrogen fluoride solution. Thesludge (or undissolved residue) contains the radioactive thorium anduranium. Dissolving the thorium and uranium in sulphuric acid andextracting it by liquid-liquid extraction or ion exchange resins canremove the radioactivity. However this, once again, has the potentialfor generating even more hazardous waste.

It is thus an object of this invention to provide a process whereby afeedstock comprising tantalum- and/or niobium-containing compounds canbe treated to recover therefrom higher purity tantalum and/or niobiumvalues, whereby these problems are addressed. In particular, it is anobject to provide a treatment process which is, as compared to theconventional treatment processes, simpler, will result in the productionof lower levels of hazardous wastes, and provides a means for dealingmore effectively with radioactive compounds. It is also an object ofthis invention to provide a means of recovering uranium values presentin the feedstock.

Thus, according to the invention, there is provided a process fortreating a feedstock comprising tantalum- and/or niobium-containingcompounds, which process includes

-   -   contacting the feedstock with a gaseous fluorinating agent,        thereby to fluorinate tantalum and/or niobium present in the        feedstock compounds; and    -   recovering the resultant fluorinated tantalum and/or niobium        compounds.

The process of the invention thus provides a means for recovering higherpurity, or even substantially pure, tantalum- and/or niobium-containingcompounds from the minerals.

Typically, both tantalum-containing and niobium-containing compounds maybe present. More particularly, the tantalum- and niobium-containingcompounds may be minerals such as those hereinbefore described, i.e.columbite (Fe,Mn)Nb₂O₆, tantalite (Fe,Mn)Ta₂O₆, and, possibly,pyrochlore (Na,Ca)Nb₂O₆(OH₁F) wherein at least some of the tantalum andniobium are present as oxides, particularly M₂O₅ where M is Ta or Nb andwhere uranium may also be present in the same mineral matrix.

The feedstock may thus comprise at least one mineral containing thetantalum- and/or niobium compounds, and, optionally, a uranium compound.

The process may thus include fluorinating a uranium compound present inthe feedstock, to obtain a fluorinated uranium compound, and recoveringthe fluorinated uranium compound. The fluorination of the uraniumcompound may take place simultaneously with the fluorination of thetantalum- and/or niobium compounds; however, instead, the fluorinationof the uranium compound can take place after the recovery of thefluorinated tantalum- and/or niobium compounds has taken place, with aresultant feedstock residue which is thus leaner in tantalum- and/orniobium compounds than the original feedstock then being contacted witha gaseous fluorinating agent to fluorinate the uranium compound.

Thus, the process of the invention also provides a means for recoveringuranium values from a feedstock, in addition to tantalum and/or niobiumvalues. The uranium values can be recovered as substantially pureuranium compounds.

The process is characterized thereby that it is carried out in thesubstantial absence of moisture, i.e. it is a dry process. In otherwords, few or no harmful and/or hazardous liquid waste products areproduced.

The gaseous fluorinating agent may comprise gaseous fluorine (F₂) and/orgaseous anhydrous hydrogen fluoride (HF), as a reactive gas, i.e. which,in a fluorinating reaction, fluorinates the tantalum- andniobium-containing compounds. The reactive gas may be pure, i.e. may bein concentrated form. Instead, however, it may be diluted with an inertcarrier gas such as nitrogen or argon. The gaseous fluorinating agentmay even, if desired, comprise a second reactive gas such as oxygen orwater vapour. Other reactive gasses, such as halide fluorides, noble gasfluorides (such as XeF₂), NF₃, or OF₂ may also be used. For the recoveryof uranium, a strong oxidative fluorinating agent such as F₂, ClF₃, NF₃gas may be used as the gaseous fluorinating agent.

The gaseous fluorinating agent, and in particular the reactive gas, thusreacts directly with the tantalum- and niobium-containing compounds tofluorinate the tantalum and niobium.

In one embodiment of the invention, the reactive gas may thus befluorine gas. The fluorinating reactions may then be in accordance withreaction (1):

M₂O₅+5F₂(g)→2MF₅+5O₂  (1)

where M is Ta or Nb.

When the feestock also comprises or contains uranium, the uranium willtypically be present as U₃O₈; the fluorinating reaction thereof may thenbe in accordance with reaction (2):

U₃O₈+9F₂→3UF₆+4O₂  (2)

wherein UF₆ is volatile

In another embodiment of the invention, the reactive gas may instead beanhydrous hydrogen fluoride gas. The fluorinating reactions may then bein accordance with reaction (3):

M₂O₅+10HF(g)→2MF₅+5H₂O  (3)

wherein M is Ta or Nb.

When the feedstock also comprises or contains uranium, the uranium willtypically, as hereinbefore indicated, be present as U₃O₈; thefluorinating reaction thereof may then be in accordance with reaction(4):

U₃O₈+8HF→UF₄+2UO₂F₂+4H₂O  (4)

wherein UF₄ and UO₂F₂ are non-volatile.

In both embodiments, the degree of fluorination may be controlled bychanging reaction parameters such as the reaction temperature, thedegree of heat imparted to the reaction, the reaction time and theproportions of reactive gas and/or carrier gas (when present) relativeto the tantalum and niobium compounds. Thus, the degree of fluorinationmay be such that oxyfluorides of tantalum and niobium, rather thanfluorides in accordance with reactions (1) and (2), are formed. In otherwords, in general, compounds of the form M_(x)O_(y)F_(z) in which M isTa or Nb, x, z are each >0 and y≧0, can be produced. It will beappreciated that when y=0, then pentafluoride compounds as hereinbeforedescribed, i.e. MF₅, are obtained. The formation of oxyfluorides can befavoured by including O₂ or H₂O as a reactive gas in addition to HF orF₂, in the fluorinating agent.

When O₂ or H₂O is present as a reactive gas, the O₂ or H₂O may be thatobtained from reactions (1) and (2) respectively.

For partial fluorination using HF as reactive gas, the reaction for Ta-and Nb-containing compounds may be that in accordance with reaction (5):

M₂O₅+HF(g)→M_(x)O_(y)F_(z)+H₂  (5)

where M is Ta or Nb.

The feedstock may be a solid ore concentrate in which the tantalumand/or niobium compounds are present in powdered or granular form. Itwill be appreciated that the solid ore concentrate will normally alsocontain other elements such as the radioactive elements uranium (U) andthorium (Th) as hereinbefore described, as well as non-radioactiveelements such as silicon (Si). Si, when present, will form fluorides,such as SiF₄, which are volatile at room temperature, and can thereforeeasily be removed from the mineral matrix. Any other metals present,such as those found in tantalite ore, for example aluminium, iron,manganese, tin, titanium, tungsten and yttrium, may also be fluorinated,and may then be removed by fractional sublimation, or will remain in themineral matrix. With HF, U and Th will substantially form non-volatileand typically thermally stable compounds, which hence remain in thesolid residue. It is not expected that the proposed process according tothis invention will form any uranium oxyfluorides other than the highlynon-volatile UO₂F₂ when the uranium in the mineral matrix is in the +6oxidation state. Other oxyfluorides of uranium that may form willthermally decompose to UO₂F₂ and UF₆. Similarly, the formation of UF₄ orThF₄ is highly unlikely, but if so, they are also non-volatile attemperatures below 1,000° C.

The recovery of the fluorinated tantalum and niobium compounds mayinclude volatilization or sublimation. Thus, when Ta and Nbpentafluorides or oxyfluorides are formed, they are volatile when thereaction temperature is sufficiently high, so that they can thus beseparated from the mineral matrix and any non-volatile compounds, suchas uranium and thorium compounds. They can thereafter be solidifiedagain, or desublimated, by allowing them to cool down. In other words,sublimation can be used to obtain the fluorinated tantalum and niobiumcompounds in purified form.

More particularly, when anhydrous HF is used as the reactive gas,constituent metal values in the ore concentrate and which are typicallyin the oxide form, will be fluorinated to their respective fluorides. Inparticular, the tantalum and niobium values are typically fluorinated totheir respective pentafluorides according to reaction (2). Thevolatilization or sublimation temperatures of tantalum pentafluoride andniobium tetrafluoride are 84° C. and 93° C. respectively, and thereforethey are very hard to separate. If the reaction temperature ismaintained above the sublimation temperatures of the pentafluorides theywill sublimate as they are formed and be separated from the mineralmatrix. If the reaction temperature is below the sublimationtemperature, a moderate subsequent temperature increase will cause thepentafluorides to sublimate. These may thereafter be separated in amulti-step fractional sublimation process by carefully selecting andmaintaining the process temperature at a level where the differentiationin sublimation rate is optimised. However, the separation efficiency ofthis method is low for obvious reasons, and multiple sublimation stepsare required for a significant isolation of the metal values.

Alternatively, the reaction conditions such as temperature, reagent(reactive gas) concentration or reagent composition may be selected suchthat both the Ta and Nb oxides are converted to the oxyfluorides. Theoxyfluorides are also volatile, but their volatilisation temperaturesrange from 160° C. to 850° C. depending on the specific species. Thus,separation and purification of oxyfluorides by fractional sublimation istherefore relatively simple and efficient.

A further alternative approach is to select the reaction conditions suchthat one of Ta or Nb is preferentially converted to the pentafluoride,while the other is converted to an oxyfluoride. The oxyfluorides arevolatile at much higher temperatures than the pentafluorides. Thus, ifone of Ta or Nb is in the pentafluoride form and the other in theoxyfluoride form, separation and purification by fractional sublimationwill become even more efficient.

Yet another route to follow, after extraction by complete fluorinationof the tantalum and niobium as pentafluorides from the mineral matrixaccording to reaction (1) or (2), is to convert selectively underappropriate conditions either the Ta or the Nb pentafluoride to theoxyfluoride by hydrolysis, leaving the other as the pentafluoride. Thesecan then be separated and purified by sublimation as described before.

Similarly and depending on the reaction and/or separation efficienciesof the relevant steps, a further alternative that may be followed, is toconvert by hydrolysis to the oxyfluorides, both the Ta and the Nbpentafluorides after being formed by complete fluorination to theoxyfluoride as before, followed by selective fluorination (e.g. with HFor F₂ or any other appropriate fluorinating agent and under appropriateconditions) one of the oxyfluorides back to the pentafluoride, leavingthe other as the oxyfluoride. Similarly, these can then easily beseparated and purified by fractional sublimation of the two molecularspecies as before. Although this may seem to add unnecessaryintermediate steps, each step contributes to the overall selectivity ofthe process, which may reduce the number of eventual sublimation steps.

The thus purified pentafluorides or oxyfluorides of Ta and Nb can beconverted to the oxides, e.g. by further hydrolysis, or directly to themetals by known appropriate reduction methods, if desired.

Once the tantalum and niobium have been removed from the feedstock, thefeedstock residue may contain uranium in the +4 oxidation state asoxides or fluorides and in the +6 oxidation state as oxides oroxyfluorides. The residue may then be treated with F₂ gas at elevatedtemperature to liberate uranium as volatile UF₆, according to thereactions:

UO₂+3F₂→UF₆+O₂  (6)

UF₄+F₂→UF₆  (7)

U₃O₈+9F₂→3UF₆+4O₂  (8)

2UO₃+6F₂→2UF₆+3O₂  (9)

UO₂F₂+2F₂→UF₆+O₂  (10)

The UF₆ is volatile already at room temperature and will thus separatefrom the residue as a gasous component, after which it can be condensedto give substantially pure UF₆.

However, when F₂ is used as the reactive gas, the mineral concentrate(in powder or granular form) may be reacted with the fluorine gas,either pure or diluted with an inert gas such as nitrogen or argon. Thereaction is preferably carried out at a temperature ranging from roomtemperature up to 1200° C., more preferably between 200° C. and 600° C.The tantalum and niobium compounds are converted to the respectivefluorides (TaF₅ and NbF₅) according to reaction (1). As hereinbeforedescribed, many of the metal impurities present in the mineral willsimultaneously, i.e. in the same processing step or stage, be convertedto fluorides as well. At room temperature these will either be volatile(e.g. SiF₄) or be non-volatile (many transition metals). In the case ofthe radioactive elements, Th will form non-volatile ThF₄ while U willform volatile UF₆. The sublimate will therefore contain stable gasessuch as SiF₄ which are easily removed, as well as TaF₅, NbF₅ and UF₆.The UF₆ can be separated from SiF₄, TaF₅ and NbF₅ by fractionaldistillation. TaF₅ and NbF₅ can be separated as above by any one of thealternative reaction routes as hereinbefore described in the HFembodiment, followed by the appropriate fractional sublimation step ormultiple steps. Once again, fluorides, oxides or metals can be obtainedby the said methods as the final product.

The tantalum and niobium pentafluorides or oxyfluorides can be treatedfurther to convert them to desired end products such as high puritymetals. Such treatment may include conversion to the oxides or reductionto pure metals.

The invention will now be described in more detail with reference to theaccompanying flow diagrams as well as the ensuing non-limiting examples.

In the drawings,

FIGS. 1 to 6 show different embodiments of a process according to theinvention for treating tantalum-containing and niobium-containingcompounds;

FIG. 7 shows, for Example 1, the first derivative of a TG curve (DTGcurve) obtained when heating TaF₅ as well as NbF₅;

FIG. 8 shows, for Example 2, DTG curves obtained when heating thereaction products of Ta₂O₅ and Nb₂O₅ with HF as described in Example 2;

FIG. 9 shows, for Example 3, the DTG curves of TaF₅ and NbO_(x)F_(y);

FIG. 10 shows, for Example 4, a graphical representation of hydrolysisof TaF₅ and NbF₅; and

FIG. 11 shows, for Example 5, volatilization/decomposition temperaturesof different M_(x)O_(y)F_(z) species, with broken lines indicatingfluorinated niobium compounds, and solid lines indicating fluorinatedtantalum compounds.

In FIGS. 1 to 6, the same or similar process steps or stages areindicated with the same reference numerals.

In FIG. 1, reference numeral 10 generally indicates a process, accordingto a first embodiment of the invention, for treating a feedstockcomprising tantalum-containing compounds and niobium-containingcompounds, according to the invention.

The process 10 includes an ore concentrate or feedstock feed line 12leading into a fluorination stage 14. A gaseous fluorinating agentaddition line 16 also leads into the stage 14. A solids withdrawal line18 leads from the stage 14 as does a room temperature volatile fluorideimpurities withdrawal line 20.

An elevated temperature volatile products transfer line 22 leads fromthe stage 14 to a fractional sublimation stage 24 with a tantalumcontaining product withdrawal line 26 as well as a niobium containingproduct withdrawal line 28 leading from the stage 24.

In use, a feedstock comprising an ore concentrate containing columbiteand tantalite as well as impurities such as uranium and silica, entersthe stage 14 along the line 12. Columbite comprises 55-78% Nb₂O₅ whiletantalite comprises 42-80% Ta₂O₅. Anhydrous HF also enters the stage 14along the line 16.

In the stage 14, the HF is initially reacted with the ore concentrate atroom temperature which results in fluorination of the tantalum andniobium values according to reaction (3). It also results influorination of uranium values to e.g. UO₂F₂ and silicon values to SiF₄.SiF₄ is volatile at room temperature, and is hence withdrawn along theline 20. The reaction temperature in the stage 14 is then increased tobetween 95° C. and 100° C. at which temperature TaF₅ and NbF₅ arevolatile and are withdrawn as a gaseous component along the line 22. Theresidue remaining in the stage 14, including the non-volatile uraniumand thorium oxyfluorides, is withdrawn along the line 18.

In the stage 24, the volatile TaF₅ and NbF₅ withdrawn from the stage 14,are subjected to fractional sublimation to obtain pure TaF₅ which iswithdrawn along the line 26 and pure NbF₅ which is withdrawn along theline 28. It will be appreciated that, instead of having only a singlefractional sublimation stage 24, a number of such stages in whichiterative fractional sublimation is carried out, may be provided.

The process 10 thus demonstrates complete fluorination of Ta and Nb withHF to pentafluorides, followed by iterative fractional sublimationthereof.

Referring to FIG. 2, reference numeral 30 generally indicates a process,according to a second embodiment of the invention, for treatingtantalum-containing compounds and niobium-containing compounds.

The process 30 is similar to the process 10, except that, in the stage14, only partial fluorination of Ta and Nb with the HF is carried out.Thus, in the stage 14 of the process 30, the formation of oxyfluoridesof Ta and Nb in accordance with reaction (5), takes place at atemperature as low as room temperature, but may instead be raised tooptimise product selectivity and distribution. The partially fluorinatedcompounds, i.e. TaO_(x)F_(y) and NbO_(x)F_(y), are volatile at elevatedtemperatures substantially higher than the sublimation temperatures ofTaF₅ and NbF₅. Typically, in the process 30, the temperature in stage 14is increased to between 100° C. and 700° C., depending on whichoxyfluoride is targeted. Further, in the stage 30, the make-up of thefluorinating agent fed into the stage 14 along the line 16 comprises amixture of an inert gas such as Ar or N₂ with the reactive gas HF, whilelow concentrations of F₂ may also be utilised. The concentration of thereactive gas HF was selected at 10% in the gas mixture. Optionally, asource of oxygen such as air may also be added. However, the optimalconcentrations for each constituent may be found by routine testing.

The process 30 thus demonstrates partial fluorination of Ta and Nbvalues with HF and an inert make-up gas with an optional source ofoxygen to produce oxyfluoride, followed by fractional sublimationthereof.

Referring to FIG. 3, reference numeral 40 generally indicates a process,according to a third embodiment of the invention, for treatingtantalum-containing compounds and niobium-containing compounds,according to the invention.

In the process 40, the stage 14 is operated such that selectivefluorination of the Ta and Nb to tantalum pentafluoride (TaF₅) andniobium oxyfluoride (NbO_(x)F_(y)) are achieved. This is effected by forexample carefully selecting and controlling the reaction parameters,such as time, temperature, gas-flow and concentration.

Thus, in the process 40, selective fluorination of Ta and Nb with HF toNbO_(x)F_(y) and TaF₅ respectively, followed by fractional sublimation,is carried out.

Referring to FIG. 4, reference numeral 50 generally indicates a process,according to a fourth embodiment of the invention, for treatingtantalum-containing compounds and niobium-containing compounds.

In the process 50, the transfer line 22 leads into a selectivehydrolysis stage 52, with a transfer line 54 leading from the stage 52to the fractional sublimation stage 24.

The stage 14 of the process 50 is operated in the same fashion as thestage 14 of the process 10. Thus, TaF₅ and NbF₅ are produced in thestage 14. These compounds pass along the line 22 into the selectivehydrolysis stage 52 where the Nb is oxidized to NbO_(x)F_(y) while theTa remains as TaF₅. It may also be feasible to find reaction conditionswhereby TaO_(x)F_(y) is formed and NbF₅ remains unreacted.

Thus, in the process 50, fluorination of Ta and Nb with HF to thecorresponding pentafluorides, followed by selective hydrolysis of theNbF₅ to NbO_(x)F_(y), followed by fractional sublimation, is carriedout.

Referring to FIG. 5, reference numeral 60 generally indicates a process,according to a fifth embodiment of the invention, for treatingtantalum-containing compounds and niobium-containing compounds.

The process 60 includes a hydrolysis stage 62, with the transfer line 22leading into the stage 62. A transfer line 64 leads from the stage 62 toa selective fluorination stage 66, with a transfer line 68 leading fromthe stage 66 to the stage 24.

In the stage 14 of the process 60, the Ta and Nb are fluorinated inaccordance with the stage 14 of the process 10, to TaF₆ and NbF₆respectively. Thereafter, in the hydrolysis stage 62, they arehydrolyzed to TaO_(x)F_(y) and NbO_(x)F_(y) respectively. Thereafter, inthe selective fluorination stage 66, the TaO_(x)F_(y) is preferentiallyfluorinated to TaF₆. Hydrolysis of both tantalum and niobiumpentafluorides in stage 62 may occur from room temperature to elevatedtemperatures to optimise a faster or more selective reaction.

Thus, in the process 60, fluorination of Ta and Nb with HF to theircorresponding pentafluorides is followed by hydrolysis of both TaF₆ andNbF₆ to TaO_(x)F_(y) and NbO_(x)F_(y) respectively, with x and y notnecessarily equal for the respective tantalum and niobium intermediates,followed by selective fluorination so that either the NbO_(x)F_(y) issubstantially converted to NbF₆, or the TaO_(x)F_(y) is substantiallyfluorinated to TaF₆ with the other component substantially remaining inthe oxyfluoride state and then followed by fractional sublimation ashereinbefore described.

When the feedstock includes uranium values, the processes 10, 30, 40, 50and 60 of FIGS. 1, 2, 3, 4 and 5 respectively, may include a secondfluorination stage 80 (shown in FIG. 1 only but which can thus, ifdesired, be present in the processes of FIG. 2, 3, 4 or 5 as well), withthe solids withdrawal line 18 from the stage 14 then leading into thestage 80. A fluorinating gas addition line 82 leads into the stage 80. AUF₆ withdrawal line 84 leads from the stage 80, as does a solidswithdrawal line 86.

In the stage 80, feedstock residue from the stage 14 and which is thuslean in tantalum and niobium values, is treated with F₂ gas enteringalong the line 82. This treatment is at elevated temperature, anduranium values present in the residue are fluorinated to form volatileUF₆, which is withdrawn along the line 84. The remainder of the solidimpurities still present are withdrawn along the line 86.

Referring to FIG. 6, reference numeral 70 generally indicates a process,according to a sixth embodiment of the invention, for treatingtantalum-containing compounds and niobium-containing compounds.

The process 70 is similar to the process 10, except that a F₂ additionline 72 leads into the stage 14 rather than the HF addition line 16. Thestages 14, 24 of the process 70 operate in substantially the samefashion as the stages 14, 24 of the process 10.

Since F₂ is used in the stage 14 rather than HF, volatile impurities,such as UF₆, can form in the stage 14 in addition to volatile SiF₄.These volatile impurities exit the stage 14 together with the volatileTa and Nb fluorides along a line 74, and are then further separated in astage 90, e.g. using fractional distillation, with UF₆ being withdrawnfrom the stage 90 along a line 92, while other volatile impurities arewithdrawn along a line 94. The Ta and Nb fluorides are withdrawn fromthe stage 90 along the line 22, which leads to the stage 24, as in FIG.1.

It will be appreciated that, if desired, the process 70 can also beadapted to render it similar to the processes 30, 40, 50 and 60hereinbefore described, except that F₂ is fed into the stage 14 ratherthan HF.

The processes 30-70 as hereinbefore described may be carried out inbatch mode. Alternatively, a continuous process is envisaged utilizing,for instance, a rotary oven operated at a temperature gradient ortemperature regions or zones to accommodate the different temperaturechanges as described as well as withdrawing the various volatile and/orsolid intermediates and products at predetermined points or zones.

In the Examples hereunder, a number of the more important steps in theprocesses of this invention as hereinbefore described, were simulatedwith substantially pure Ta and Nb pentafluorides and oxides.

EXAMPLE 1

When both tantalum and niobium oxides are fluorinated to theirpentafluoride forms, their respective sublimation temperatures aretypically 84° C. and 93° C. FIG. 7 shows the first derivative of a TGcurve (normally referred to as a DTG curve) obtained when heating TaF₅as well as NbF₅. As seen from FIG. 7, sublimation of niobiumpentafluoride occurs first followed by sublimation of tantalumpentafluoride.

EXAMPLE 2

In a simulation of the embodiment of the invention as described byprocess 30 in FIG. 2, niobium and tantalum oxides are separately treatedwith HF to form oxyfluorides. In this Example, both oxides were treatedwith a 1:10 HF:N₂ mixture at 40° C. Spectroscopy confirmed the presenceof oxyfluoride compounds. When these products are then heated, thefractional sublimation property is best shown by overlaying their DTGcurves—see FIG. 8.

In FIG. 8 it is shown that no significant (volatilization) mass lossoccurs for the niobium compound below 144° C., while a significant partof the tantalum product (at least 30%) sublimates. By re-treatment ofthe solid residue, this process may be iteratively continued,systematically removing niobium species.

EXAMPLE 3

FIG. 9 shows the DTG curves of TaF₅ and NbO_(x)F_(y) which are theproducts expected in the embodiment described by the process 40 in FIG.3.

There is about 70° C. difference in volatilization temperatures, whichwould make separation of these compounds simple.

EXAMPLE 4

Hydrolysis of tantalum pentafluoride occurs at a much slower rate (at astudied temperature of 40° C.) than niobium pentafluoride (FIG. 10),which supports the possibility of selectively hydrolyzing the niobiumfluoride to the oxyfloride.

EXAMPLE 5

A mixture of Ta₂O₅ and Nb₂O₅ was prepared at a mass ratio of about 1:1.This mixture was partially fluorinated with gaseous HF at 40° C.according to reaction (5) for a period of 3 hours. From the fluorinatedproduct four samples were taken (see Table 1) and were heated to atemperature of about 165° C., which is the onset temperature forsublimation of a niobium oxyfluoride species (FIG. 11), but well belowthe onset temperature for the analogous tantalum species under constantnitrogen flow. Ta:Nb ratio measurements with Inductively Coupled Plasma(ICP) analysis before and after each run are shown in Table 1.

Though a maximum separation efficiency of 36.0% was achieved for Run 4,it will be appreciated that with optimising the process parametersand/or cascading several separation steps, a much greater level ofseparation may be achieved.

TABLE 1 Ta:Nb ratios for treated and untreated samples using ICP valuesTa:Nb ratio Ta:Nb ratio Separation Untreated Treated Efficiency Run 11.02 0.78 23.5% Run 2 1.02 0.68 33.3% Run 3 1.08 0.77 28.9% Run 4 1.250.80 36.0%

1. A process for treating a feedstock comprising tantalum- and/orniobium-containing compounds, which process includes contacting thefeedstock with a gaseous fluorinating agent, thereby to fluorinatetantalum and/or niobium present in the feedstock compounds; andrecovering the resultant fluorinated tantalum and/or niobium compounds.2. A process according to claim 1, wherein the feedstock comprises atleast one mineral containing the tantalum- and/or niobium compounds, andwherein the tantalum- and/or niobium-containing compounds compriseoxides of the formula M₂O₅ where M is Ta or Nb.
 3. A process accordingto claim 2, which is characterized thereby that it is carried out in thesubstantial absence of moisture, so that it is a dry process, with fewharmful and/or hazardous liquid waste products being produced.
 4. Aprocess according to claim 2 or claim 3, wherein the gaseousfluorinating agent comprises gaseous fluorine and/or gaseous anhydroushydrogen fluoride as a reactive gas which, in a fluorinating reaction,fluorinates the tantalum- and niobium-containing compounds.
 5. A processaccording to claim 4, wherein the reactive gas is fluorine gas, with thefluorinating reaction proceeding in accordance with reaction (1):M₂O₅+5F₂(g)→2MF₅+5O₂  (1) where M is Ta or Nb.
 6. A process according toclaim 4, wherein the reactive gas is anhydrous hydrogen fluoride gas,with the fluorinating reaction proceeding in accordance with reaction(2):M₂O₅+10HF(g)→2MF₅+5H₂O  (2) where N is Ta or Nb.
 7. A process accordingto claim 4, wherein the degree of fluorination is controlled such thatoxyfluoride compounds of tantalum and niobium, in accordance withformula M_(x)O_(y)F_(z) in which M is Ta or Nb, x and z are each >0, andy≧0, are produced.
 8. A process according to claim 7, wherein thefluorinating agent includes, in addition to the reactive gas comprisinggaseous fluorine (F₂) and/or gaseous anhydrous hydrogen fluoride andwhich is hence a first reactive gas, also a second reactive gascomprising oxygen and/or water vapour, thereby to promote formation ofthe oxyfluoride compounds.
 9. A process according to claim 4, whereinthe reactive gas is gaseous anhydrous hydrogen fluoride, with partialfluorination being achieved in accordance with reaction (3):M₂O₅+HF(g)→M_(x)O_(y)F_(z)+H₂  (5) where M is Ta or Nb, x and z areeach >0, and y≧0.
 10. A process according to any one of claims 2 to 4inclusive, wherein the feedstock is a solid ore concentrate in which thetantalum and/or niobium compounds are present in powder or granularform, with the concentrate also containing radioactive uranium andthorium as well as non-radioactive silicon, with the silicon reactingwith the fluorinating agent to form a silicon fluoride, while theuranium and thorium react with the fluorinating agent to formnon-volatile and thermally stable fluorides and/or oxyfluorides.
 11. Aprocess according to any one of claims 2 to 10 inclusive, wherein therecovery of the fluorinated tantalum and niobium compounds includesvolatilization of the compounds at elevated temperature so that they arethereby separated from non-volatile feedstock residue, whereafter thevolatilized compounds are desublimated, by allowing them to cool down.12. A process according to claim 11, wherein the fluorinated tantalumcompounds are separated from the fluorinated niobium compounds byfractional sublimation.
 13. A process according to any one of claims 1to 4 inclusive, which includes selecting the reaction conditions suchthat one of tantalum or niobium is preferentially converted to apentafluoride compound of the formula MF₅ where M=Ta or Nb, while theother is converted to an oxyfluoride compound, with the oxyfluoridecompound being volatile at a higher temperature than the pentafluoridecompound, and separating and purifying the pentafluoride and oxyfluoridecompounds by fractional sublimation.
 14. A process according to any oneof claims 1 to 4 inclusive, which includes fluorinating the tantalum andniobium compounds in the feedstock to volatile pentafluoride compoundsof the formula MF₅ where M=Ta or Nb; withdrawing the volatilepentafluoride compounds; converting selectively either the tantalum orthe niobium pentafluoride to the oxyfluoride by hydrolysis, leaving theother as the pentafluoride compound; and separating and purifying theresultant compounds by fractional sublimation.
 15. A process accordingto any one of claims 2 to 4 inclusive, wherein the feedstock contains,in addition to the tantalum and/or niobium compounds, also a uraniumcompound.
 16. A process according to claim 15, wherein the reactive gasis fluorine gas which reacts, at elevated temperature and at the sametime that it reacts with the tantalum and/or niobium compounds tofluorinate them, with the uranium compound to form volatile uraniumhexafluoride (UF₆), with the gaseous uranium hexafluoride then beingremoved together with the gaseous fluorinated tantalum and/or niobiumcompounds that are formed.
 17. A process according to claim 16, whereinthe gaseous uranium hexafluoride that is formed is separated from thegaseous fluorinated tantalum and/or niobium compounds.
 18. A processaccording to claim 15 wherein, after recovery of the fluorinatedtantalum and/or niobium compounds has taken place, a resultant feedstockresidue which is thus leaner in tantalum and/or niobium compounds thanthe feedstock is then contacted at elevated temperature with a gaseousfluorinating agent selected from F₂, ClF₃ and NF₃, to fluorinate theuranium compound.
 19. A process according to claim 18, wherein thefluorine compound is U₃O₈, which is fluorinated to volatile UF₆, withthe process including separating the volatile UF₆ from the resultantresidue.